WO2003004554A1 - Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy - Google Patents
Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy Download PDFInfo
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- WO2003004554A1 WO2003004554A1 PCT/US2002/019267 US0219267W WO03004554A1 WO 2003004554 A1 WO2003004554 A1 WO 2003004554A1 US 0219267 W US0219267 W US 0219267W WO 03004554 A1 WO03004554 A1 WO 03004554A1
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- sorbitol
- dimethylbenzylidene
- methylbenzylidene
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- 0 *c1c(*)c(*)c(C2OC(C(CO)O)C3OC(c4c(*)c(*)c(*)c(O*)c4*)OCC3O2)c(*)c1* Chemical compound *c1c(*)c(*)c(C2OC(C(CO)O)C3OC(c4c(*)c(*)c(*)c(O*)c4*)OCC3O2)c(*)c1* 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
Definitions
- thermoplastic additives that induce simultaneously low clarity and high nucleation efficacy.
- Such additives include combinations of certain bicyclic salts (which by themselves induce very high nucleation efficacy) and thermoplastic clarifying agents, including certain dibenzylidene sorbitol acetals and derivatives (hereinafter collectively referred to as "DBSs”)(which alone provide very low haze measurements and thus highly desirable clarity characteristics).
- thermoplastic nucleators such as sodium benzoate and sodium 2,2'-mefhylene-bis-(4,6-di- tert-butylphenyl) phosphate provide relatively high peak crystallization temperatures, but do not combine synergistically with clarifiers, such as DBSs, to provide the same results as for the inventive combination of bicyclic salts and DBSs.
- Thermoplastic compositions as well as thermoplastic additive packages comprising such inventive nucleator compounds, as well as methods of producing polypropylene compositions and articles made therefrom, are also contemplated within this invention.
- thermoplastic is intended to mean a polymeric material that will melt upon exposure to sufficient heat but will retain its solidified state, but not prior shape without use of a mold or like article, upon sufficient cooling. Specifically, as well, such a term is intended solely to encompass polymers meeting such a broad definition that also exhibit either crystalline or semi-crystalline morphology upon cooling after melt- formation. Particular types of polymers contemplated within such a definition include, without limitation, polyolefms (such as polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (such as nylon), polyurethanes, polyesters (such as polyethylene terephthalate), and the like (as well as ariy combinations thereof).
- Thermoplastics have been utilized in a variety of end-use applications, including storage containers, medical devices, food packages, plastic tubes and pipes, shelving units, and the like. Such base compositions, however, must exhibit certain physical characteristics in order to permit widespread use. Specifically within polyolefms, for example, uniformity in arrangement of crystals upon crystallization is a necessity to provide an effective, durable, and versatile polyolefin article. In order to achieve such desirable physical properties, it has been known that certain compounds and compositions provide nucleation sites for polyolefin crystal growth during molding or fabrication. Generally, compositions containing such nucleating compounds crystallize at a much faster rate than unnucleated polyolefin. Such crystallization at higher temperatures results in reduced fabrication cycle times and a variety of improvements in physical properties, such as, as one example, stiffness.
- nucleators Such compounds and compositions that provide faster and or higher polymer crystallization temperatures are thus popularly known as nucleators.
- Such, compounds are, as their name suggests, utilized to provide nucleation sites for crystal growth during cooling of a thermoplastic molten formulation.
- the presence of such nucleation sites results in a larger number of smaller crystals.
- clarification of the target thermoplastic may also be achieved, although excellent clarity is not always a result. The more unifonn, and preferably smaller, the crystal size, the less light is scattered. In such a manner, the clarity of the thermoplastic article itself can be improved.
- thermoplastics being very important to the thermoplastic industry in order to provide enhanced physical properties and/or faster processing to the target thermoplastic article or composition, is highly desirable in order to reduce costs and provide improved plastics in terms of durability, impact resistance, and the like.
- thermoplastic e.g., polyolefin
- an additive that induces low haze measurements within the ultimate polyolefin product.
- a combination of high nucleation efficacy and low haze is highly desirable; however, to date there are very few alternatives individually to provide effective low haze or high peak crystallization temperatures within the target polyolefin and no real alternatives that provides an effective combination of such characteristics.
- the most effective clarifying agent known to the industry and available commercially at this time is also a type of nucleator, namely dibenzylidene sorbitol acetal derivative compounds (again, "DBSs").
- Such compounds are typical nucleator compounds, particularly for polypropylene end-products, and include, without limitation.
- Compounds such as 1,3-0- 2,4-bis(3,4-dimethylbenzylidene) sorbitol, available from Milliken Chemical under the trade name Millad® 3988 (hereinafter referred to as 3,4-DMDBS), l,3-O-2,4-bis(p- methylbenzylidene) sorbitol, also available from Milliken & Company under the trade name Millad® 3940 (hereinafter referred to as 7-MDBS).
- 3-DMDBS Milliken Chemical under the trade name Millad® 3988
- 7-MDBS Millad® 3940
- such compounds provide excellent clarification and relatively effective nucleation characteristics for target polypropylenes and other polyolefins.
- the peak crystallization temperatures provided by such compounds for the aforementioned polyolefins e.g., polypropylene
- Such nucleators include sodium benzoate, sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl) phosphate (from Asalii Denka Kogyo K.K., known as and hereinafter referred to as NA-11), aluminum bis[2,2'- methylene-bis-(4,6-di-tert-butylphenyl)phosphate] with lithium myristate (also from Asahi Denka Kogyo K.K., which is understood to be known as and hereinafter referred to as NA- 21), talc, and the like.
- Such compounds all impart the desirable high polyolefin crystallization temperatures indicative of excellent nucleation capabilities.
- bicyclic dicarboxylic acid and salts have been taught as polyolefin nucleating agents as well within Patent Cooperation Treaty Application WO 98/29494, 98/29495 and 98/29496, all assigned to Minnesota Mining and Manufacturing.
- the best working examples of this technology are embodied in disodium bicyclo[2.2.1]heptene dicarboxylate and camphanic acid.
- the efficacy of nucleating agents is typically measured by the peak crystallization temperature of the polymer compositions containing such nucleating agents.
- a high polymer peak crystallization is indicative of high nucleation efficacy, which generally translates into fast processing cycle time and more desirable physical properties, such as stiffness/impact balance, etc., for the fabricated parts.
- Compounds mentioned above all impart relatively high ⁇ polyolefin crystallization temperatures; however, each also exhibits its own drawback for large-scale industrial applications.
- the effective nucleating compounds exhibit a very high peak crystallization temperature, for example, above 125°C within homopolymer polypropylene (wherein such peak crystallization temperatures are measured by differential scanning calorimetry in accordance with ASTM Test Method D3417-99 modified to measure at heating and cooling rates of 20°C/minute).
- peak crystallization temperatures are measured by differential scanning calorimetry in accordance with ASTM Test Method D3417-99 modified to measure at heating and cooling rates of 20°C/minute.
- a simultaneous clarity of below about 14% (as measured by ASTM D 1003-92) for the same homopolymer propylene at such high peak crystallization temperature levels has, again, heretofore been unattainable.
- Such a combination of nucleation efficiency and clarity is, again, highly desired and as of yet impossible to provide on a widespread scale for thermoplastics, polyolefins generally, and most specifically poypropylenes.
- nucleating/clarifying compositions include high polymer crystallization temperature and good clarity, there are a number of other performance characteristics important for the practical use of such nucleating/clarifying compositions.
- typical polyolefin e.g., polypropylene, polyethylene, and the like
- calcium stearate compatibility is particularly important.
- nucleator compounds noted above such as sodium benzoate, NA-11, disodium bicyclo[2.2.1] heptene dicarboxylate
- nucleator compounds are generally provided in powder or granular form to the polyolefin manufacturer, and since uniform small particles of nucleating agents are imperative to provide the requisite unifonii dispersion and performance, such compounds must remain as small particles through storage.
- Certain nucleators such as sodium benzoate, exhibit high degrees of hygroscopicity such that the powders made therefrom hydrate easily resulting in particulate agglomeration.
- Such agglomerated particles may require further milling or other processing for deagglomeration in order to achieve the desired uniform dispersion within the target thermoplastic.
- unwanted agglomeration due to hydration may also cause feeding and/or handling problems for the user.
- thermoplastic polyolefin, and succinctly, polypropylene
- an object of the invention is to provide a thermoplastic additive composition that simultaneously induces high levels of nucleation efficiency as well as low degrees of haze (and thus excellent clarity) therefor within target thermoplastic articles. Additionally, it is an object of this invention to provide such a nucleator/clarifier additive composition that may be used in various polyolefin media for use in myriad end-uses.
- this invention encompasses a composition comprising at least one saturated bicyclic carboxylic salt and at least one thermoplastic clarifying agent, most notably, the broad class of any dibenzylidene alditol acetal or derivative thereof.
- thermoplastic comprising such a composition and a method of producing such a thermoplastic comprising said composition are also encompassed within this invention.
- Such a method includes the steps of a) providing a molten thermoplastic formulation; b) introducing to such formulation and mixing therein a composition comprising at least one saturated bicyclic carboxylic salt and at least thermoplastic clarifying agent, most notably, the broad class of any dibenzylidene sorbitol acetal or derivative thereof; and c) allowing the resultant composition of step "b" to cool into a thermoplastic article.
- thermoplastic clarifying agent is intended to encompass any compound that provides improved clarity through haze measurement reduction of a thermoplastic by at least 10% in comparison with such a thermoplastic wherein no clarifying agent is present.
- Such compounds include DBSs, NA-11, NA-21, and any other compounds that meet this description.
- As the required saturated bicyclic dicarboxylic salts have not been utilized in combination with such specific clarifying agents in the past, there is no teaching or fair suggestion of such an inventive combination within the thermoplasticindustry or prior art. Such a combination of specific types of compounds has been found to induce the aforementioned desirous qualities and characteristics of high nucleation efficacy and low haze simultaneously within thermoplastic media.
- saturated bicyclic carboxylic acid salt compounds are defined as organic compounds that contain two or more rings wherein at least two of the said rings share at least two nonadjacent atoms and do not exhibit any double bonds therein.
- novel nucleator compounds include the metal or organic salts of saturated [2.2.1] bicyclic dicarboxylates, and most preferably of these types of compounds conforming to Formula (I)
- M ⁇ and M 2 are the same or different, or M ⁇ and M are combined to from a single moiety, and are independently selected from the group consisting of metal or organic cations
- R l3 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are individually selected from the group consisting of hydrogen, -C 9 alkyl, hydroxyl, -C 9 alkoxy, -C 9 alkyleneoxy, amine, and C 1 -C 9 alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal -C 9 carbocyclic.
- the metal cations are selected from the group consisting of calcium, strontium, barium, magnesium, aluminum, silver, sodium, lithium, rubidium, potassium, and the like. Witliin that scope, group I and group II metal ions are generally preferred. Among the group I and II cations, sodium, potassium, calcium and strontium are preferred, wherein sodium and calcium are most preferred. Furthermore, the Mi and M 2 groups may also be combined to form a single metal cation (such as calcium, strontium, barium, magnesium, aluminum, and the like). Although this invention encompasses all stereochemical configurations of such compounds, the cis configuration is preferred wherein cis-endo is the most preferred embodiment. The preferred embodiment polyolefin articles and additive compositions for polyolefin formulations comprising at least one of such compounds are also encompassed within this invention.
- Dibenzylidene alditol acetal or any derivative thereof may be introduced within the inventive fluid dispersion and method.
- such compounds are represented by the structure of Formula (II):
- R9 R9
- the DBS compound may be symmetrical or asymmetrical as well.
- the dibenzylidene alditol acetal compound is symmetrical and exhibits 3,4-disubstitution of the same or different pendant groups, although such a limitation is not required.
- dibenzylidene sorbitol acetal or derivatives include, as merely examples: l,3:2,4-dibenzylidene sorbitol; l,3:2,4-di(p-methylbenzylidene) sorbitol; l,3:2,4-di(p- chlorobenzyhdene) sorbitol; l,3:2,4-di(2,4-dimethyldibenzylidene) sorbitol; l,3:2,4-di(p- ethylbenzylidene) sorbitol, l,3:2,4-di(3,4-dimethyldibenzylidene) sorbitol, abbreviated as 3,4- DMBS, l,3-O-(3,4-dichlorobenzylidene):2,4-O-(3,4-dimethylbenzylidene) sorbitol, 1,3-0- (3,4
- DBS derivative is 3,4-DMBS.
- a diacetal compound as well as any type of DBS system, may be produced through the condensation reaction between two moles of an aromatic aldehyde and one mole of apolyhydric alcohol.
- the aldehyde and polyhydric alcohol are generally provided in the reaction mixture in a ratio from 1:1 to 4:1, preferably 1.5:1 to 2.5:1; respectively.
- the aromatic aldehydes are single or fused double ring aldehydes having at least one unsaturated hydrocarbon ring, and include benzaldehyde, naphthaldehyde, indan aldehyde and tetrahydronaphthaldehyde (tetralin aldehyde).
- the aromatic aldehydes may be unsubstituted or have from one to five substituent groups selected from C 1- alkyl, C 1-4 alkoxy, hydroxy, halogen, C 1-6 alkylthio, C 1-6 alkylsulfoxy, C 3-5 alkylene forming a carbocyclic ring with adjacent carbon atoms on an unsaturated hydrocarbon ring, carboxyl, (C ⁇ -C 20 alkyloxy)carbonyl, ( -C 20 alkyloxy)ethyloxycarbonyl, (CrC 12 alkyl)phenyl, halogenated phenyl, ( -C 1 alkoxy)phenyl, (Ci-C ⁇ .2 alkyloxy)ethyloxyethyloxycarbonyl and alkyloxy)ethyloxy- ethyloxyethyloxycarbonyl groups.
- the aromatic aldehyde is selected from unsubstituted benzaldehyde, benzaldehyde having from one to three substituent groups selected from C 1- alkyl, halogen and C 3-5 alkylene forming a carbocyclic ring with adjacent carbon atoms on an unsaturated hydrocarbon ring, including p-methyl, p-ethyl, 2,4-dimethyl, 3,4-dimethyl and 2,4,5-trimethyl benzaldehyde, 5-indan aldehyde and 5', 6', T, 8'-tetrahydro- 2-naphthaldehyde.
- Aromatal aldehydes may be provided and will result in a distribution of diacetals having the same or different aromatic components, referred to as symmetric and asymmetric diacetals, respectively.
- the aromatic aldehydes typically react with the polyhydric alcohol to form acetals in the 1 :3 and 2:4 positions.
- triacetals formed by the condensation of three moles of an aromatic aldehyde and one mole of a polyhydric alcohol having six or more hydroxyl groups.
- the triacetals are typically formed at the 1:3, 2:4 and 5:6 positions of the alcohol.
- the polyhydric alcohols have five or more hydroxyl groups.
- the sugar alcohols represented by the formula HOCH 2 (CHOH) n CH 2 OH, where n 3-5, have been found to be especially useful.
- the polyhydric alcohol is a pentahydric or hexahydric alcohol, most preferably xylitol or sorbitol.
- the polyhydric alcohol can be added to the reaction mixture as a solid, molten liquid, or as an aqueous solution.
- the polyhydric alcohol is concentrated to a syrup by the azeotropic removal of water with a hydrophobic solvent, such as cyclohexane, prior to addition.
- inventive salts provide excellent mechanical properties for polyolefin articles without the need for extra fillers and rigidifying additives, and desirable processing characteristics such as improved (shorter) cycle time.
- the compositions also exhibit inducement of very low haze measurements for target thermoplastics, particularly the same polyolefins as noted above for the nucleation properties.
- highly transparent, efficiently nucleated polyolefins e.g., polypropylenes
- these inventive compositions exhibit other highly desirable characteristics.
- the inventive compositions show much improved hygroscopicity comparing to prior art and thus granular or powder formulations of such unsaturated bicylic carboxylic acid salt nucleating agents (e.g., they do not agglomerate or clump together). Additionally, the inventive compositions do not interact deleteriously with commonly found calcium stearate additives. Also, the resultant thermoplastics exhibit desirable flexural modulus properties as well.
- the saturated bicyclic nucleating agent(s) exhibit favorable synergistic effects with DBSs.
- the blends Upon mixing with such DBS (or derivative) compounds, the blends exhibit exceptional nucelation efficacy (as measured by polymer peak crystallization temperature) and excellent clarity (as measured in haze).
- the unsaturated bicylic compound mixed with DBSs fails to provide the such improved synergistic effects (as noted below within the Examples). No other typical nucleating agent provides such synergistic effect either (again, see the Examples below).
- inventive compositions are thus added within the target polyolefin in an amount from about 50 ppm to about 20,000 ppm by weight in order to provide the aforementioned beneficial characteristics, most preferably from about 200 to about 4000 ppm. Higher levels, e.g., 50% or more by weight, may also be used in a masterbatch formulation.
- Optional additives within the inventive salt-containing composition, or within the final polyolefin article made therewith, may include plasticizers, antistatic agents, stabilizers, ultraviolet absorbers, and other similar standard polyolefin thermoplastic additives.
- additives may also be present within this composition, most notably antioxidants, antistatic compounds, antimicrobials (preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company), perfumes, chlorine scavengers, and the like.
- antioxidants preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company
- antimicrobials preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company
- perfumes preferably chlorine scavengers, and the like.
- the individual components are present in amounts from about 10 ppm to about 15,000 ppm each; preferably, from about 100 ppm to about 5,000 ppm each; more preferably from about 200 ppm to about 3,500 ppm each; and most preferably between about 500 ppm and 2,500 ppm each.
- polyolefin or polyolefin resin is intended to encompass any materials comprised of at least one polyolefin compound.
- Preferred examples include isotactic and syndiotactic polypropylene, polyethylene, poly(4-methyl)pentene, polybutylene, and any blends or copolymers thereof, whether high or low density in composition.
- the polyolefin polymers of the present invention may include aliphatic polyolefins and copolymers made from at least one aliphatic olefin and one or more ethylenically unsaturated co-monomers.
- the co-monomers if present, will be provided in a minor amount, e.g., about 10 percent or less or even about 5 percent or less, based upon the weight of the polyolefin (e.g. random copolymer polypropylene), but copolymers containing up to 25% or more of the co- monomer (e.g., impact copolymers) are also envisaged.
- Other polymers or rubber such as EPDM or EPR
- Such co-monomers may serve to assist in clarity improvement of the polyolefin, or they may function to improve other properties of the polymer.
- Other examples include acrylic acid and vinyl acetate, etc.
- olefin polymers whose transparency can be improved conveniently according to the present invention are polymers and copolymers of aliphatic monoolefins containing 2 to about 6 carbon atoms which have an average molecular weight of from about 10,000 to about 2,000,000, preferably from about 30,000 to about 300,000, such as, without limitation, polyethylene, linear low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, crystalline ethylene propylene copolymer, poly(l-butene), polymethylpentene, 1-hexene, 1-octene, and vinyl cyclohexane.
- the polyolefins of the present invention may be described as basically linear, regular polymers that may optionally contain side chains such as are found, for instance, in conventional low density polyethylene.
- the nucleating agents of the present invention are not restricted to polyolefins, and may also give beneficial nucleation properties to polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), as well as polyamides such as Nylon 6, Nylon 6,6, and others.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- any thermoplastic composition having some crystalline content may be improved with the nucleating agents of the present invention.
- thermoplastic articles of the present invention maybe obtained by adding the inventive composition of saturated bicyclic dicarboxylic acid salt (or combination of salts or composition comprising such salts) and DBS to the thermoplastic polymer or copolymer and merely mixing the resultant composition by any suitable means.
- a concentrate containing as much as about 20 percent by weight of the inventive composition in a polyolefin masterbatch comprising the required acid scavenger may be prepared and be subsequently mixed with the target resin.
- inventive compositions may be present in any type of standard thermoplastic (e.g., polyolefin, most preferably) additive form, including, without limitation, powder, prill, agglomerate, liquid suspension, and the like, particularly comprising dispersion aids such as polyolefin (e.g., polyethylene) waxes, stearate esters of glycerin, montan waxes, mineral oil, and the like.
- any form may be exhibited by such a combination or composition including such combination made from blending, agglomeration, compaction, and/or extrusion.
- small particle size below 30 microns on average, more specifically, below 15 microns on average
- powders provide better flow properties for the additive and thus are more easily handled and introduced within the target theraioplastic formulation.
- composition may then be processed and fabricated by any number of different techniques, including, without limitation, injection molding, injection blow molding, injection stretch blow molding, injection rotational molding, extrusion, extrusion blow molding, sheet extrusion, film extrusion, cast film extrusion, foam extrusion, thermoforming (such as into films, blown-films, biaxially oriented films), thin wall injection molding, and the like into a fabricated article.
- injection molding injection blow molding, injection stretch blow molding, injection rotational molding, extrusion, extrusion blow molding, sheet extrusion, film extrusion, cast film extrusion, foam extrusion, thermoforming (such as into films, blown-films, biaxially oriented films), thin wall injection molding, and the like into a fabricated article.
- Thermoplastic compositions were produced comprising the additives from the Examples above and sample homopolymer polypropylene (HP) or polypropylene random copolymer resin plaques, produced dry blended in a Welex mixer at -2000 rpm, extruded through a single screw extruder at 400-450° F, and pelletized. Accordingly, one kilogram batches of target polypropylene were produced in accordance with the following compositions:
- the base HP (having an isotacticity determined to be between about 96 and 99% through xylene solubles analysis) and all additives were weighed and then blended in a Welex mixer for 1 minute at about 1600 rpm. All samples were then melt compounded on a Killion single screw extruder at a ramped temperature from about 204° to 232°C through four heating zones. The melt temperature upon exit of the extruder die was about 246°C. The screw had a diameter of 2.54 cm and a length/diameter ratio of 24: 1. Upon melting the molten polymer was filtered through a 60 mesh (250 micron) screen.
- Plaques of the target polypropylene were then made through extrusion into an Arburg 25 ton injection molder.
- the molder was set at a temperature anywhere between 190 and 260°C, with a range of 190 to 240°C preferred, most preferably from about 200 to 230°C.
- the plaques had dimensions of about 51 mm X 76 mm X 1.27 mm, and the mold had a mirror finish which was transferred to the individual plaques.
- the mold cooling circulating water was controlled at a temperature of about 25°C. Testing for nucleating effects and other important criteria were accomplished through the formation of plaques of clarified polypropylene thermoplastic resin. These plaques were formed through the process outlined above with the specific compositions listed above in the above Table.
- plaque formulations are, of course, merely preferred embodiments of the mventive article and method and are not intended to limit the scope of this invention.
- the resultant plaques were then tested for peak crystallization temperatures (by Differential Scanning Calorimetry). Crystallization is important in order to determine the time needed to form a solid article from the molten polyolefin composition.
- a polyolefin such as polypropylene has a crystallization temperature of about 110°C at a cooling rate of 20 °C/min.
- the best nucleator compound added will invariably also provide the highest crystallization temperature for the final polyolefin product.
- the nucleation composition efficacy particular polymer pealc crystallization temperature (T c ), was evaluated by using DSC according to ASTM D-794-85. To measure these temperatures, the specific polypropylene composition was heated from 60°C to 220°C at a rate of 20°C per minute to produce a molten formulation and held at the peak temperature for 2 minutes. At that time, the temperature was then lowered at a rate of 20°C per minute until it reached the starting temperature of 60°C.
- the crystallization temperature was thus measured as the peak maximum during the crystallization exotherm.
- the clarification performance of the nucleators was measured using ASTM D 1003-92.
- the data show that the blends of DMDBS with commercial nucleators exhibit less or no enhance in polymer pealc crystallization temperature and generally significantly higher haze comparing to the inventive blends.
- the blends of DMDBS with nucleator from example 2 do not cause significant deterioration in clarity performance of the DBS derivative, but fail to provide enhancement in nucleation efficacy.
- Tl/2 crystallization half-time
- the inventive blends also exhibit improved flexual modulus when comparing to DBS alone.
- the data is shown in following table: EXPERIMENTAL TABLE 8
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Abstract
Description
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP02742175A EP1409579B1 (en) | 2001-07-03 | 2002-06-18 | Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy |
DE60216927T DE60216927T2 (en) | 2001-07-03 | 2002-06-18 | DETERGENT FORMULATIONS FOR THERMOPLASTICS WITH VERY HIGH NUCLEAR EFFICIENCY |
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US09/898,359 | 2001-07-03 | ||
US09/898,359 US6521685B1 (en) | 2001-07-03 | 2001-07-03 | Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy |
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EP (1) | EP1409579B1 (en) |
CN (1) | CN1238409C (en) |
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JP6789818B2 (en) | 2014-04-10 | 2020-11-25 | スリーエム イノベイティブ プロパティズ カンパニー | Fibers and articles containing the fibers |
GB2531301B (en) * | 2014-10-15 | 2016-08-31 | Njc Europe Ltd | Additive composition, method of blending same and a low haze polyolefin material and preparation thereof |
CN105622627A (en) * | 2016-02-03 | 2016-06-01 | 苏州亚培克生物科技有限公司 | DBS polyolefin nucleating agent and preparation method and application thereof |
CN111961027B (en) * | 2020-08-18 | 2023-11-17 | 上海齐润新材料有限公司 | Composition and method for preparing transparent articles at low temperature |
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- 2002-06-18 EP EP02742175A patent/EP1409579B1/en not_active Expired - Lifetime
- 2002-06-18 AT AT02742175T patent/ATE348856T1/en not_active IP Right Cessation
- 2002-06-18 DE DE60216927T patent/DE60216927T2/en not_active Expired - Lifetime
- 2002-06-18 CN CNB028135628A patent/CN1238409C/en not_active Expired - Lifetime
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WO2005040259A1 (en) | 2003-10-03 | 2005-05-06 | Milliken & Company | Improved nucleating additive formulations of bicyclo[2.2.1]heptane dicarboxylate salts |
EP1668071A1 (en) * | 2003-10-03 | 2006-06-14 | Milliken & Company | Improved nucleating additive formulations of bicyclo 2.2.1|heptane dicarboxylate salts |
EP1668071A4 (en) * | 2003-10-03 | 2009-04-22 | Milliken & Co | Improved nucleating additive formulations of bicyclo 2.2.1 heptane dicarboxylate salts |
EP3109274A1 (en) | 2015-06-23 | 2016-12-28 | Omya International AG | Surface treated filler material product for alpha-nucleation of polyolefins |
US10654986B2 (en) | 2015-06-23 | 2020-05-19 | Omya International Ag | Surface treated filler material product for alpha-nucleation of polyolefins |
CN110317364A (en) * | 2019-07-25 | 2019-10-11 | 赣州蓝风科技有限公司 | Nucleating agent and its preparation method and application |
Also Published As
Publication number | Publication date |
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EP1409579A4 (en) | 2005-03-09 |
CN1524108A (en) | 2004-08-25 |
US6521685B1 (en) | 2003-02-18 |
CN1238409C (en) | 2006-01-25 |
DE60216927D1 (en) | 2007-02-01 |
EP1409579A1 (en) | 2004-04-21 |
EP1409579B1 (en) | 2006-12-20 |
ATE348856T1 (en) | 2007-01-15 |
DE60216927T2 (en) | 2007-10-18 |
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